Magnetism and Luminescence of a MOF with Linear Mn3 Nodes Derived from an Emissive Terthiophene-Based Imidazole Linker

A new terthiophene-based imidazole luminophore 5,5’-(1H-thieno[3,4-d]imidazole-4,6-diyl)bis(thiophene-2-carboxylic acid) (TIBTCH2, 5) was synthesized in one step from previously reported 4,6-di(thiophen-2-yl)-1H-thieno[3,4-d]imidazole (DTTI, 4), and their photophysical properties were studied and compared accordingly. Under solvothermal conditions, reacting 5 with Mn(OAc)2 yielded a new three-dimensional metal-organic framework (MOF, 6) which was structurally defined by single-crystal X-ray diffraction. In 6, all Mn(II) ions octahedrally bind to carboxylate-O atoms to form a linear Mn3 secondary building unit (SBU) that contains three distinct coordination modes. Importantly, 6 exhibits dual functional properties of ligand-based emission and metal-based magnetic behaviors.

Influence of linkers on the Kuratowski-type secondary building unit in nickel single-site MOFs for ethylene oligomerization catalysis: a computational study

Ni-Kuratowski-type MOFs were studied computationally for ethylene oligomerization and the catalytic performance of sterically different linkers was elucidated.

Highly dispersed secondary building unit-stabilized binary metal center on a hierarchical porous carbon matrix for enhanced oxygen evolution reaction

MOF-derived carbon matrix with binary metal center shows high electrochemical activity toward OER.

Scrutinizing ligand exchange reactions in the formation of the precious group metal–organic framework RuII,II-HKUST-1: the impact of diruthenium tetracarboxylate precursor and modulator choice

The high surface area univalent Ru(ii) analogue of HKUST-1 (Ru3BTC2; BTC = 1,3,5 benzendicarboxylate) is synthesized by the coordination modulated controlled secondary building unit approach.

Combining valproate and bipyridyl ligands to construct a 0D core-shell Zn5(μ3-OH)2 cluster and a 2D layered coordination network with a [Zn3(μ3-OH)]2 SBU

Starting from the proposed zinc carboxylate cluster tetrakis(μ-2-propylpentanoato)dizinc(II), Zn2(μ2-valp)4 (I), of valproic acid, a branched short-chain fatty acid, and bipyridine ligands, two new mixed-ligand coordination compounds, namely, bis(2,2′-bipyridine)di-μ3-hydroxido-hexakis(μ-2-propylpentanoato)bis(2-propylpentanoato)pentazinc(II), [Zn5(C8H15O2)8(OH)2(C10H8N2)2] (II), and poly[[bis(μ-4,4′-bipyridine)di-μ3-hydroxido-octakis(μ-2-propylpentanoato)bis(2-propylpentanoato)hexazinc(II)] dimethylformamide disolvate], {[Zn6(C8H15O2)10(OH)2(C10H8N2)2]·2C3H7NO} n (III), were synthesized. Compound II is a core-shell-type zero-dimensional discrete Zn5(μ3-OH)2 metal–organic cluster with Zn ions in double-triangle arrangements that share one Zn ion coincident with an inversion centre. The cluster contains three crystallographically non-equivalent Zn ions exhibiting three different coordination geometries (tetrahedral, square pyramidal and octahedral). The cluster cores are well separated and embedded in a protective shell of the aliphatic branched short chains of valproate. As a result, there is no specific interaction between the discrete clusters. Conversely, compound III, a 2D layered coordination network with a secondary building unit (SBU), is formed by Zn6(μ3-OH)2 clusters exhibiting a chair-like hexagonal arrangement. This SBU is formed from two Zn3(μ3-OH) trimers related by inversion symmetry and connected by two syn–anti bridging carboxylate groups. Each SBU is connected by four 4,4′-bipyridine ligands producing a 63-hcb net topology. 2D coordination layers are sandwiched within layers of dimethylformamide molecules that do not interact strongly with the network due to the hydrophobic protection provided by the valproate ligands.